Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
  • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
  • H01B3/445—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/032—Organic insulating material consisting of one material
  • H05K1/034—Organic insulating material consisting of one material containing halogen
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0104—Properties and characteristics in general
  • H05K2201/0116—Porous, e.g. foam
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—Materials
  • H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0206—Materials
  • H05K2201/0209—Inorganic, non-metallic particles
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0206—Materials
  • H05K2201/0212—Resin particles
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0242—Shape of an individual particle
  • H05K2201/0254—Microballoons or hollow filler particles

Definitions

• This invention relates to a composite material of low dielectric constant, having electric properties improved by incorporation therein of minute hollow spheres.
• PTFE polytetrafluoroethylene
• porous PTFE since the PTFE in a molten state exhibits extremely high viscosity, it defies adoption of any of the conventional methods such as physical foaming by the forced introduction of an inert gas or chemical foaming by the use of a foaming agent which have heretofore been popularly practiced on thermoplastic resins or other fluorocarbon resins. Thus, the production of porous PTFE has no alternative but to rely on some special method or other.
• porous PTFE porous PTFE
• the porous articles obtained by these methods invariably have intercommunicating pores. They function advantageously as filters, for example.
• the insulators have a disadvantage that the mechanical strength, particularly the strength to resist compression, manifested by the insulators sharply decreases, the dimensional stability notably declines, and the stability of electric properties diminishes in proportion as the porosity of the porous articles increases.
• this invention aims to solve the problem to provide a composite material of low dielectric constant formed in porous texture with PTFE, which com­posite article suffers only slight change in mechanical strength due to an increase in porosity, maintains electric properties stably, and permits easy control of porosity and easy forming during the course of pro­duction.
• the invention contem strictlyplates a composite material of low dielectric constant, having minute hollow spheres made of insulating material and dispersed in a fibrous polytetrafluoroethylene.
• the fibrous polytetrafluoroethylene used in the present invention is a resin possessing a fine fibrous texture and obtained when unsintered PTFE particles are shaped under the conditions capable of exerting shear strength such as rolling.
• the minute hollow spheres to be used in the present invention are made of an insulating material such as glass, plastic, or rubber and are desired to possess particle diameters in the range of 1 to 300 ⁇ m.
• an insulating material such as glass, plastic, or rubber
• those made of glass having a silicon dioxide content of not less than 80 % prove to be particularly desirable.
• the hollow spheres have such a gas as N2 or CO2 sealed therein, the composite material has low specific gravity and low dielectric constant.
• the amount of the minute hollow spheres to be incorporated in the composite material is not particularly restricted but may be properly selected to suit the material of the spheres or the use for which the composite material is intended.
• the composite material When the composite material is used as an electric insulating material, for example, it is desirable from the standpoint of effect of incorporation to select this amount approximately in the range of 50 to 95 % by weight based on the amount of the composite material.
• the minute hollow spheres may be given a surface treatment with a coupling agent in advance of use.
• the characteristic of creep inherent in the polytetrafluoroethylene enables the composite material to occlude a large bulk of minute hollow spheres therein. Further, since minute hollow spheres of low dielectric constant made of such insulating material as glass or plastic and having such a gas as N2 or CO2 sealed therein are dispersed in a fibrous polytetrafluoroethylene, what is consequently obtained is a polytetrafluoroethylene composition of a porous texture containing discrete pores. The composite material, therefore, possesses very low dielectric constant and high mechanical strength.
• the fine PTFE powder destined to serve as a raw material for the fi­ brous PTFE composite assumes a fine fibrous texture when it is subjected in an unsintered state to shear strength as when it is extruded through a die during the course of extrusion, drawn out with a roll, or stirred with blades, for example.
• the resin in a state containing a liquid lubricant, has the nature of easily assuming a fibrous form and undergoing plastic deformation and, therefore, can be formed readily by rolling or extrusion, for example.
• the formed article consequently obtained, even in an unfired state, is possessed of fairly high mechanical strength because the PTFE particles are oriented after the pattern of fibers and are intertwined to give rise to a fibrous texture during the course of forming.
• the resin is allowed to retain its inherent nature of yielding to plastic deformation, because the individual PTFE particles in the unsintered state are not completely integrated. This explains why the composite material can be formed by rolling or extrusion.
• the composite material is prevented from appreciably losing mechanical strength, because of the fibrous texture formed of PTFE.
• fluorocarbon resin such as, for example, an ethylene tetrafluoride­propylene hexafluoride copolymer resin suffers from sharp rise of melt viscosity and fall of flowability when it is mixed with minute hollow spheres.
• the upper limit of the amount of minute hollow spheres tolerated to be incorporated in this resin is ap­proximately 10 % by weight at most.
• This invention originating in the finding that the fine unsintered PTFE powder is easily converted into fibers and plastically deformed even after it has incorporated therein a large bulk of minute hollow spheres and, moreover, the formed article of the resin consequently obtained possesses the nature of retaining proper mechanical strength, aims to allow the composite material to acquire low dielectric constant by causing minute hollow spheres of low dielectric constant to be retained as in voids between the fibers of the PTFE resin now in a fibrous tex­ture.
• the PTFE forms a fibrous texture and the minute hollow spheres are dispersed and lodged in the voids between the fibres of the PTFE.
• the two components of the mixture are united strongly with the minute hollow spheres held fast between the fibers of PTFE.
• the composite material may be used in an unsintered state or in an incompletely sintered state.
• the minute hollow spheres When the minute hollow spheres are treated with a coupling agent, this treatment imparts oil-appetency to the surface of the minute hollow spheres. They, consequently, exhibit increases affinity for the fibrous polytetrafluoroethylene which forms the matrix of the composite mate­rial and are highly effective in enhancing the mechanical strength of the finally produced composite material.
• the aged mixture was stirred for slight conversion into fibers and drawn out with a roll to promote the conversion into fibers, forming to a sheet 0,15 mm in thickness.
• the sheet was heated to expel the liquid lubricant and then sintered at 370°C for three minutes to obtain a composite material of low dielectric constant as contemplated by the pre­sent invention.
• the sheet of composite material thus obtained exhibited appreciably high electric properties as evinced by a dielectric constant of 1,5, enjoyed freedom from such drawbacks as collapse of pores or loss of dimensional stability which are frequently observed in the conventional porous PTFE sheet containing intercommunicating pores, and manifested notably improvement in the stability of electric properties.
• a composite material was obtained by following the procedure of Example 1, excepting the minute hollow spheres of glass (produced by Fuji Davison Chemical Co., Ltd. and marketed under product code of "H-101"), used in 70 percent by weight, were given a surface treatment with 1 percent by weight of a silane coupling agent (produced by Daihachi Chemical Co., Ltd., and marketed under product code of "RT-18E") before use.
• the minute hollow spheres of glass produced by Fuji Davison Chemical Co., Ltd. and marketed under product code of "H-101”
• a silane coupling agent produced by Daihachi Chemical Co., Ltd., and marketed under product code of "RT-18E
• the composite material thus produced possessed a dielectric constant of 1,8, a value higher than that of the composite material of Example 1.
• a titanate coupling agent can be used as effective­ly as the silane coupling agent.
• the kind and the amount of the coupling agent are selected so as to suit the material of the minute hollow spheres and the use for which the composite material of low dielectric constant is intended. Where the virtue of low dielectric constant con­stitutes a main target, the amount of the coupling agent to be used is desired to be as small as possible. At times, the use of the coupling agent may be omitted.
• the minute hollow spheres there can be cited glass, minute mineral balloons origi­nating in volcanic ashes, plastics, and rubber.
• One member or a mixture of two or more members selected from the group of substance enume­rated above can be used.
• those made of glass having the silicon dioxide content thereof increased to a level above 80% as by an acid treatment prove to be particularly desirable because of their notably low dielectric constant of 1,2.
• a plastic material such as polyimide type resin or fluorine type rubber which enjoys high thermal stability in due consideration of the intense heat to be used during the course of sintering.
• a plastic material such as polyethy­lene or polystyrene which has no very high thermal stability may be used.
• the particles diameter and the amount of use of these minute hollow spheres can be properly selected so as to suit the use for which the composite material is intended and the substance of which the minute hollow spheres are made. Generally, the particle diameter is desired to fall in the range of 1 to 300 ⁇ m.
• the amount of minute hollow spheres is in the range of 50 to 95 wt % according to the effect of incorporation of the spheres and/or the mechanical strength of the product.
• the unsintered PTFE has the nature of assuming a fine fibrous texture on exposure to shear strength. This conversion of the unsintered PTFE into fibers is facilitated by the addition of a liquid lubricant. For the sake of this invention, this conversion of the PTFE into fibers constitutes itself one of the important requirements.
• the stable retention of the large bulk of minute hollow spheres in the composite material is materialized by improving the mechanical strength of PTFE as the matrix resin owing to the conversion thereof into fibers.
• the unsintered PTFE containing the minute hollow spheres therefore, must be formed by the method of extrusion, the method of rolling, or the combination of both methods to be described below, so as to suit the use for which the finally produced composite material is intended.
• the forming effected by any of the methods described above is essential strictlyly carried out at a temperature not exceeding 327°C, the melting point of PTFE, preferably at a temperature near normal room temperature.
• the PTFE mixture which has been formed in a prescribed shape by any of the methods described above is heated for expulsion of the liquid lubricant and then sintered to give rise to a composite material of low dielectric constant as aimed at by this invention.
• the composite material may be produced in an incompletely sintered form or in a completely unsintered state, depending on the use for which the composite material is intended.
• the conventional porous PTFE material must be given a surface treatment with an ammonia solution of sodium metal or with a naphthalene solution of tetrahydrofuran so as to aquire improved adhesiveness or wettability before it is subjected to a treatment of adhesion or plating.
• the composite material of low dielectric constant ac­cording to the present invention particularly when the amount of minute hollow spheres incorporated therein is increased, brings about an effect of obviating the necessity for such a surface treatment as mentioned above.
• the composite material of this invention has minute hollow spheres of light dielectric constant dispersed in a matrix of fibrous ethylene tetrafluoride resin and, therefore, exhibits a low dielectric constant.
• the dielectric constant of the produced compo­site material can be controlled to a desired level by selecting the par­ticle diameter and the amount of incorporation of the minute hollow spheres.
• the composite material provided by this invention is used advantageously as an electric insulating material.
• the composite material possesses a porous texture containing dis­crete pores.
• the composite material is produced in a form incorporating the minute hollow spheres in an increased amount to lower the dielectric constant, it enjoys highly desirable dimensional stability because it is not easily crushed unlike the conventional countertype, i.e. a composite material of porous polytetrafluoroethylen containing inter­communicating pores. Owing to the high dimensional stability, the composite material enjoys a great advantage that the electric properties thereof are retained intact.
• the produced composite material is allowed to manifest adhesiveness and wettability on the surface thereof.
• this composite material is used as an insulating material in a printed board, for example, it brings about an advantage that it can be safely and effectively plated without requiring the through hole part thereof to be given any special surface treatment.
• the present invention need not be limited to the working examples cited above but may be modified or altered variously as by the variation in the amount of use and the particle diameter of the minute hollow spheres, without departing from the technical idea of the invention.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Power Engineering (AREA)
• Physics & Mathematics (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Manufacturing & Machinery (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
• Moulding By Coating Moulds (AREA)
• Organic Insulating Materials (AREA)
• Inorganic Insulating Materials (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

Applications Claiming Priority (2)

Publications (2)

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ID=16658463

Family Applications (1)

Country Status (5)

Cited By (14)

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• 1987
  • 1987-08-28 JP JP62214604A patent/JPS6460648A/ja active Granted
• 1988
  • 1988-05-04 KR KR1019880005212A patent/KR920000221B1/ko not_active Expired
  • 1988-08-01 GB GB8818243A patent/GB2209167B/en not_active Expired - Lifetime
  • 1988-08-04 EP EP88112746A patent/EP0304699A3/de not_active Withdrawn
  • 1988-08-04 DE DE198888112746T patent/DE304699T1/de active Pending

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